QUICK Tans yh DAMAGE AND CORROSION MECHANISMS - API 571 E4 + Damage tolerance + DM character and appearance + DMs listed by API'571 category + Explanatory figures and photographs + Links with FFP categories for damage evaluation www.matthews-training.co.uk acne PEE Tay SUE esFIG P1 MATTHEWS TRAINING PROVIDES AN ONLINE EXAM PREPARATION PROGRAMME FOR THE API 571 INDIVIDUAL CERTIFICATION PROGRAMME (ICP) EXAMINATION ‘THE EXAMINATION ‘The API571 ICP examination certificate is recognised worldwide as a demonstration of knowledge of damage mechanisms in the oil/petrochemical industry. * Examinations are held three times per year and can be attended over a two-week window period at API-contracted examination centres situated in most countries of the world. * The examination comprises 70 closed-book questions with a fixed pass mark of 70% * Entry to the API571 ICP examination Is open to anyone who can meet the API entry criteria. Candidates do not have to have previously passed an API 510/570/653 certificate. (OUR ONLINE EXAM PREPARATION TRAINING PROGRAMME ‘The Matthews Training online training programme is structured specifically to prepare candidates for the API 571 ICP examination. * Online training programme available for 10-12 weeks before each scheduled exain window * Programme includes introduction to all DMs followed by extensive interactive question sets and mock examinations, * Contact us via our website wwwwmatthews-training.co.uk for programme dates and prices.FIG P1 (CONT) COURSE PREPARATION READ THE COURSE FACTSHEETS (F1 to F3) Module HI Mock Exam 1 Course completion Feedback and Records mp | rwCONTENTS SECTION A: Introduction ‘An introduction to API (RP) 571 Mechanical properties of metals - essential background Factors that encourage corrosion How to use this guide SECTION B: Damage Mechanisms: Mechanical/Metallurgical Degradation (Group 1) + Brittle facture Mechanical/vibration fatigue ‘Thermal fatigue Erosion/corrosion Short-term overheating ‘Thermal shock Steam blanketing/departure from nucleate boiling (ONB) Dissimilar weld metal (DWM) cracking Strain ageing Cavitation SECTION C: Damage Mechanisms: Loss of Wall Thickness (LOWT) (Group 2) Galvanic corrosion Atmospheric corrosion Corrosion under insulation (CU!) Cooling water corrosion Microbiologically induced corrosion (MIC) Soil corrosion Dealloying Graphitic corrosion SECTION D: Damage Mechanisms: High Temperature (> 400°F) (Group 3) Creep rupture High-temperature oxidation High-temperature sulfidation Carburisation/decarburisation www.matthews-training.co.uk 10 19 21 25 28 29 31 32 33 34 35 37 39 a a 46 49 50 53 55 56 57 59 64 67 6 n© Metal dusting nt * — Fuel ash corrosion/slagging “a * High-temperature Ho/H,S corrosion 7 » 475°C (885°F) ferrite embrittlement 79 + Temper embrittlement 81 * Graphitisation and spheroidisation 83 * Sigma phase embrittlement. 85 * — Reheat cracking 86 * High-temperature hydrogen attack (HTHA) 87 * — Nitriding 89 SECTION E: Damage Mechanisms: Environmentally Assisted Cracking (EAC) (Group 4) ” © Environmentally induced cracking (EAC) 94 * — Chloride SCC 100 * — Corrosion fatigue 101 * Caustic SCC (embrittlement) 102 * Polythionic acid SCC (PASC) 103 * Wet H2S damage mechanisms 106 | © Hydrogen-induced cracking (HIC) 109 ‘+ Stress oriented hydrogen-induced cracking { {SOHIC) 110 + Sulfide stress cracking (SCC) am | . HF stress cracking M2 ‘+ Carbonate alkaline stress corrosion cracking (ACSC) 13 | * Ammonia SCC of copper alloys 115 * Liquid metal embrittlement (LME) 116 SECTION F: Damage Mechanisms: I Refinery Chemical Acid/Alkaline LOWT (Group 5) 119 + Refinery-specific LOWT damage mechanisms. 122 * — Caustic corrosion 128 * Boiler condensate/CO; corrosion 130 | * Flue gas dewpoint corrosion 133 + Amine corrosion 134 Abbreviations 135 Reference codes 139 | 2 ‘www.matthews-training,co.ukSe i binie KK { ; AN INTRODUCTION TO API (RP) 571 | API571 (formally called API RP 571) is one of the most useful of the API codes. Although it is aimed mainly at refineries, it is also in use across many different process industries, where it is | accepted as a base reference document about damage mechan- isms (DMs). Unlike many API documents, API 571 is not equip- ment-specific it is equally relevant to vessels, pipework, tanks and auxiliary items such as valves and fittings. This gives it very wide application. With this, however, comes the problem of size. Over recent editions, API 571 has grown to several hundred pages, almost all of which are directly relevant to the subject of identifying (and then avoiding) damage mechanisms - so there is | __ little information of ‘secondary importance’ that can be conveni- ently ignored. I Who is API 571 intended for? API 571 is intended for practical use by inspectors and engineers rather than corrosion specialists and metallurgists. It does not pretend to be an authoritative scientific coverage of the subject, = which means that you can expect it to contain simplification | (and oceasional inaccuracies). On balance, the benefits of these simplifications far outweigh any negative aspects, they just make | API-571 what it is, a reference document that you can actually | use. APL 571 is found in regular use in oil refineries worldwide. Its content has been adapted for use in numerous other purposes | = most RBI software relies heavily on the DMs and related information, catalogued in AP| 571. Inspection plans or written | schemes of examination (WSEs) also regularly use its DM break- | down as a starting point for specifying inspection activities to find them. As an inspection engineer, there is little you need tomh eee know about DMs that is not included somewhere in API 571, so it is a very useful document to have knowledge of. How is API 571 structured? Fig A1 shows the structure of AP! 571. Note how the list of DMs (there are a lot of them, 66 in total) is subdivided into five separate blocks .The nature of this categorisation owes more to API's viewpoint than either their regularity of occurrence, or scientific rigour — its main purpose is to divide them into more manageable groups. There is some scientific basis to the split, but as with all corrosion definitions, boundaries between them will always be a little artificial, and open to technical opinion and interpretation. In this guide we will look at the main ones, changing the order slightly, to make for easier reading. How does API 571 fit in with other API codes? As well as acting as a general reference document for DMs, API 571 also describes itself as a document linked to API (RP) 579 Fitness for service (FFS) assessment. Fig A2 shows the idea. In reality this link is perhaps not quite as close as described - an assessment to API 579 does require knowledge of the physical size and extent of the damage being assessed, but there is less of a link with the precise nature of the DM that actually caused it. In some ways this is good news; API 579 is a large and complex document (1000+ pages) ~ treat it as a completely separate subject, interesting in itself but not essential to understand as part of an appreciation of API 571.SECTION A: Introduction FIG Al I The Basic Structure of API 571 4.2 Mechanical and metallurgical DMs 4.3 Uniform or local metal loss DMs DMs are subdivided @ little artificially) into 5 blocks 44 High-temperature corrosion DMs 4.5 Environmentassisted cracking DMs 5.1 Specific refinery DMs 5.1.1 Uniform or local metal loss 5.1.2 Environment- assisted cracking 5.1.3 Other DMs. | ‘Section numbers shown refer to the 2011 edition Continued Over...| mh eee ete ere eee ! FIG Al J Each DM section is subdivided like this Prevention/ mitigationsro mtn mi FIG A2 API 571 links with other codes ‘API/ASME New equipment has no corrosion Construction Codes ‘or damage e.g. ASME VII/B31.3 Equipment goes into service pant ST) Meet tne auipment in (Ms) service Equipment is damaged beyond the limits of its construction code Le. it is out of code Level 1 FIS assessment calculations are oe [2 es Ny, é used to determine if the it ‘equipment is still safe to use. Three levels of assessment are Level 3 available| mh ee ee | MECHANICAL PROPERTIES OF METALS — I ESSENTIAL BACKGROUND Metal properties? What is all this about? Metal mechanical properties pop up in the discussion of almost every one of the DMs that make up API 571.The core information you need on metal mechanical properties is fairly simple and finite - you don’t need any metallurgy books (and you certainly don't need to be a metallurgist). Unfortunately, details of the metal mechanical properties that | you need to understand better for API 571 are not actually provided in API 571, they are covered in API 577 with its elaborate title Welding Process, inspection and Metallurgy. | Metal properties - what you need to know I There is a fine dividing line between the mechanical properties of a metal (how it behaves) and its corresponding chemical composition (what it is made of). At our simplified level of | analysis it is the mechanical properties that are most important. Yes, the elemental chemical composition ultimately makes the metal what it is, but that is more chemistry and metallurgy - | subjects for another day. Fig A3, the ‘keystone properties’ diagram shows the four main | mechanical properties that we need to know about, i.e. ‘+ Strength. How strong it is, to resist tensile stresses. | + Ductility. Will it undergo ‘plastic deformation’ (permanent | stretch ~ like toffee) when it is put under tensile stress?.SECTION As Irodacton mh * Toughness. Can it resist impact loads with cracking in a brittle manner like glass without stretching or deforming? If it is not tough, itis brittle, * Hardness. Can it resist surface indentation from a hard object (e.g. like diamond), or is it soft (like coal)? Are these different properties, or are they linked together? Both. For API 571 purposes it helps to think of them as being very separate properties, each acting on its own, being affected by Gifferent things, and having different ways of measurement and testing. There are a few links of course, but think of them as loose correlation-type relationships rather than hard and fast tules. Let's look at them in turn (see Fig A3). Strength When a small tensile load is applied, all metals stretch elastically, They will return to their original length when the load is removed. As the load is increased the metal reaches a point where it ceases to be ‘elastic’ but starts to stretch (deform) Plastically, i.e. it won't go back to its original length. This is the yield point (5,). Increasing the load further takes the metal to a Point where it starts to flow and ‘neck’ prior to eventually break- ing. This is the (ultimate) tensile strength (5) Pressure equipment design prefers materials with high yield strength, as they can be thinner. Typically a low-carbon steel with a yield of say 30 ksi (30,000 psi) will be designed to operate at an allowable stress (5) of about 3 x yield, i.e. 20 ksi, to give an adequate ‘safety margin’ for hydrotesting and unexpected loads. Simplistically then, high yield strength permits a high allowable! K ie a anos Cc sansa I FIG A3 ‘The Four ‘Keystone’ Mechanical : Properties of Metals ' sre, 7 A fouls 6 foot pounds Yield ape! KH strengih | / : mors S.. ‘ ‘cama ¥ ‘Tensile test Surface indentation test Betore test C= Diamond or ball under an applied force terest Jp, SD | 8 Elongationi SECTION: tavoducton Ki | stress to be used, leading to thinner material sections and lower | weight. ‘Toughness (or brittleness) We have decided that strong is good. Sadly, this has limitations. ‘When materials get stronger they tend to become more brittle {the same as calling them Jess tough). So, although the high strength is good at resisting static loads, when any impact loads come along (vibration, shock, etc.) the metal decides not to fail by stretching plastically to failure, but ignores that route alto- gether and instead fails by crack propagation, without much deformation at all. This is termed brittle fracture, generally bad | News during activities such as hydrotesting equipment or operat- ing equipment at low temperatures, which makes brittleness | worse (see Fig A4 again). Toughness is determined using an impact (Charpy or Izod) test | and measured in Joules or foot-pounds (in the USA). So: | « High toughness resists brittle fracture (which is a form of crack propagation), Ductility Ductility is the ability to deform plastically (when a high stress is | feached). This results in a more ‘stable and predictable’ method of failure than cracking, thereby making ductility a generally | desirable property. It is measured by calculating the % elonga- | _ tion and % reduction of cross-sectional area of the same test piece during the tensile ‘strength’ test. Unfortunately, too much ductility brings a problem. A high- | ductility metal (such as copper) will tend also to have lowmw (Quek Guide to Damage and Corrosion Mechaniss~APLSTL l | FIG A4 f The Four Keystone Properties — Their Effect I ‘Think of this as a ‘continuum: diagram with continuous variation from left to right Duetile and Tough* Strong, Hard and Brittle : += i Metal fails by: Metal fails by: \ * Plastic deformation: * Crack propagation * Grains sliding over each + Abrittle mechanism 1 other * Necking/reduction in area { *Note that ductility and toughness are NOT the same thing. Even though they may have a similar effect. I ‘Think of it like this: ! + Ductility is the ability of metal ‘grains’ to slide and I deform THEN | * When grains can slide and deform, they are quite happy to do this around the tips of small cracks, which | prevents them propagating into big cracks \ So, the result is TOUGHNESS |I Caer nm i strength. Strength falls as ductility increases. Once again, the | relationship is not tidily linear, and varies a lot between different materials, but the correlation is pretty good, particularly for ! commonly used low-carbon steels. So: * Ductility is good as it reduces the chance of brittle fracture BUT | With high ductility comes a reduction in yield strength. Hardness | You can think of hardness as a property of the surface of a metal — the resistance to surface indentation (or scratching if you want a cruder view). It is therefore a completely different property to | strength, ductility and toughness, which together are more con- cerned with how the body of a material responds to loads. | Hardness has several scales of measurement (Vickers, Brinel, Rockwell and Knoop). High hardness is a desirable property in | metals that have to resist wear (cutting, drilling, etc.) or as a result of relative motion (rotating items with bearing surfaces | and similar). In general: «Hard metals are strong (good) BUT, THE DOWNSIDE IS * They can also be brittle (bad). In practice, heat treatments such as tempering can be used to decrease the brittleness (i.e. increase toughness) at the expensemi {eA Sten Garde eile of some loss of hardness, but it is a fine balance. Metal cold- chisels and other tools involving impact are made like this. What influences these four ‘keystone properties’ of metals? Fig AS shows the things that influence a metal’s properties. It is a complex picture, which varies from metal to metal, and their thousands of potential alloy combinations. For our purposes it is sufficient to rely on the general message of Fig A5. We can then be ready to recognise specific causes and effects as they are raised in API 571. You will find this more efficient than getting too deeply involved in the complex metal- lurgy relationships that are waiting to distract you if you look too deeply. Damage mechanisms Damage mechanisms (DMs) divide broadly into those involving corrosion and those driven mainly by mechanical factors (e.g. vibration or thermal cycling) on some type of embrittlement and crack propagation mechanism. Fig A6 shows the situation. Some DMs involve a bit of both types, so classifications can vary, depending on technical viewpoint. This guide follows the broad principles of API 571 (see Fig A6), which is as logical as any other.I SECTION A: Introduction i I FIG A5 What Influences a Metal’s Properties? NS Chemical composition I ‘renath : | — Bey | 02% GC 1% Heat treatment Grain structure caalag/ailen ] of the alloy manufactureK Pexlote noah aaceese naan age FIG A6 Damage Mechanisms -v- Corrosion Mechanisms - A Simple View - DAMAGE MECHANISMS CORROSION NON-CORROSION MECHANISMS MECHANISMS Alltypes of corrosion Le rasan tai [Creep |— Reheat cracking These do not involve a corrosion mechanismseh itn mw | | FACTORS THAT ENCOURAGE CORROSION | Of the many types and sub-types of corrosion that affect metals, most are driven by one of more of the following corrosion factors: * The presence of oxygen (O2) + Heat = Contact by aggressive chemical compounds * Stress, of some type. The factors invariably work in combination, with their cumula- | _ tive effect varying for different materials. This is what makes corrosion engineering such a wide subject. Fig A7 shows the | situation.mn ee eee ees FIG AZ Factors that Encourage Corrosion a Heat attack —— (mainly high temperatures) Metal oxides are weak, increasing stresses in the Molecular movement good metal that remains Increases witl temperature Corrosion (of many different types) + How much * How fast A Chemical attack Stress attack (lH) (tensile, fatigue, shear, ete) Encourages the production of oxides + These factors invartably act together, producing a cumulative effect,sro. wm HOW TO USE THIS GUIDE DM groupings This guide follows the basic structure of API 571 in dividing DMs into groups based predominately on their effect, and the failure mode (FM) that they cause. Fig A8 shows a summary of the groups, with broad technical justification of their differences. Failure mode (FM) logos Each DM page contains a logo showing the types of failure mode (or modes) associated with that particular DM. These are shown in Fig A9. Some have multiple logos, indicating that the DM can have several possible FM outcomes, depending on exactly how ‘or when it occurs, or combines with other associated DMs. Damage mechanism photographs Photographs shown in this guide show typical features of the DMs they describe. In a real engineering situation DM appear- ance can be very varied, so these photos do not pretend to be a unique example of what the DM will always look like.mw ee tee eT FIG A8 DM Groupings - Technical Justification — NOTE THESE KEY POINTS Cena ‘+ These are not really corrosion PSone eons as such, many lead to failure by cracking or weakening. Brera + ‘These are true corrosion mechanisms, many oxidation driven + Temperature is <400°F (so that (DH sveyare not hightemperature DMs) + Physically the corrosion ean have many diferent appearances + Higher temperatures >400°F ‘combine with chemical attack a ees to produce some serious DMs, ees * Creep is not corrosion, so this group excludes creep + This refers to the process environment, not the external surroundings, (HF - dvitaiiures are preceded by cracking, encouraged by the aggressive chemical ‘compounds. + Characterised by aeid or Group 5: alkaline (caustic) attack ea ey + Mainly experienced in oil Per Rem industry downstream (refinery) plant.SECTION A:tntvoduction mh FIG A9 DM/FM Logos Used in this Guide PITTIN + Deep, narrow pits + Can be isolated or grouped + Surface breaking SCALING * Corrosion product forms on surface * Corrosion may continue [ underneath + Acts as heat insulator WEAKENING + Loss of tensile strength + Eneourages ductile faihure + Reduced hardness LOSS OF WALL THICKNESS + May be uniform or localised + Loss of cross-section ‘encourages tensile failure * May be accompanied by pitting. resulting in leakage CRACKING + Pailure by crack propagation in brittle microstructure ‘+ Embrittlement can be caused by low temperature or chemical attack + Unpredictable, catastrophic l and dangerousSECTION B: Damage Mechanisms: Mechanical/Metallurgical Degradation (Group 1)scones con il GROUP 1 DMs MECHANICAL/METALLURGICAL DEGRADATION Brittle fracture Mechanical/vibration fatigue Thermal fatigue Erosion/corrosion Short-term overheating Thermal shock Steam blanketing/departure from nucleate boiling (DNB) Dissimilar weld metal (DMW) cracking Strain ageing Cavitationro] {Quick Gulde to Damage and Corrosion Mechanisms -APIST1 f [ BRITTLE FRACTURE | Description Appearance I Cracking with little plastic Single or multiple cracking with deformation flat fracture faces Inspection; VT or surface NDE (PT, MT, ECT). Difficult to detect in early stages. I Critical factors: Caused by operating below the ductile-to- brittle transition temperatures for a material. | Encouraged by: | * Carbon and chromium content * Hardness (inadequate PWHT) | «Thick sections and 3-D stresses. FFP/Severity: Can cause unexpected catastrophic failure. Cracking is a dangerous, unpredictable DM. References: API 571 (4.2.7): See also process-based embrittlement DMs.Fe ee ae een eee eT KK , MECHANICAL/VIBRATION FATIGUE | Description Appearance Crack propagation after * Initial failure area is flat with multiple stress cycles below possible ‘striations’ or beach the yield point marks’ * Final failure is ductile. May show 45° shear lips Inspection: VT or surface NDE PT/MT/ECT to find cracks in early stages | ‘www.matthews-training.co.uk »mh ick Gide to Damage and Corrosion Mecham APL S71 l ee) Critical factors: Heavily dependent on: | + Number/amplitude of stress cycles | * Component geometry; sharp features, changes of section, weld defects causing | stress concentrations. FFP/Severity: Almost impossible to predict accurately under real vibration conditions. Causes unpredictable | catastrophic failures. * Hard/brittle materials are most difficultto | predict. | References: API571 (4.2.16-17)scone ntaciatsinncine i , THERMAL FATIGUE | Description Appearance Cracking under repeated Uneven ‘dagger-shaped’ cracks | thermal cycles Oxide residue on crack faces | Inspection: \VTor surface NDE (PT, MT, ECT). Cracks start on | the micro scale and can be difficult to detect in the early stages. | Gritical factors: * Temperature swings > 93°C (200°F) are sufficient to start cracks. + Made worse by combination with | mechanical/vibration fatigue conditions. «Can propagate manufacturing weld defects. | FFP/Severity: Can cause unexpected catastrophic failure. I * Cracking is a dangerous, unpredictable DM. References: API 571 (4.2a).KK Quick Gude to Darnaye and Corrosion Mechanlas -APIS71 ! EROSION/CORROSION Description Appearance I Wearing away of metals by _Localised grooving ~ often deep high-velocity process fluids and sharp-edged I os Inspection: VT from the eroded side | UT from reverse side or RT in profile view Critical factors: * Increase with high velocities and suspended solids content. \ ‘+ Common on pump impellers, heat exchangers and agitated vessels. FFP/Severity: —_Localised wall thinning/grooving often causes. | leak-before-break References: API 571 (4.2.14). Assessment to API 579 (Sec. 5) |Svoe nas eb nye neet ie ee y mh | SHORT-TERM OVERHEATING Description Appearance Weakening due to short-term Visible deformation/bulging exposure to temperatures _leading to principal stress above those recommended failure for the material cm | paw ! ae Inspection: VT of the component for bulges etc. | Physical measurement of tubes, headers, Critical factors: * Can occur in all materials operating above their safe temperature range. | * Caused by plant upsets, fluid restrictions, burner misadjustment, missing refractory. | * Thick sections and 3-D stresses. | FFP/Severity: Bulging causes wall thinning, weakening of the material leading to stress failure (tube splits). | Extreme overheating can cause surface cracking and more rapid catastrophic failure. References: API 571 (4.2.10). Assessment to API 579mh pa apd ra eT THERMAL SHOCK I Description Appearance I Uneven expansion caused by Generally cracking, with (usually rapid) temperature accompanying distortion differentials (not the absolute depending on the component temperature itself) geometry Inspection: Tor surface NDE (PT, MT, ECT) for surface- 1 breaking cracks Unpredictable and difficult to locate I Critical factors: « Most common cause is cold liquid Il contacting a hotter metal surface ‘+ Castings and brittle materials are I particularly vulnerable. FFP/Severity: Difficult to assess reliably in embrittled materials. { Always a risk of catastrophic cracking failure if ductility is reduced References: API 571 (4.2.13) IParle eae eee ee ane aegeipean ee KK STEAM BLANKETING (ALSO CALLED DEPARTURE | FROM NUCLEATE BOILING (DNB) Description Appearance Steam bubbles form a blanket Causes sharp-edged principal inside a tube. Heat flow is (hoop stress) failure as a result interrupted causing of the local overheating overheating Inspection: Critical factors: | FFP/Severity: | References: VT for tube bulging Normally only found after tube-burst has occurred Fracture faces show plastic deformation * Most commonly a problem with excessive heat flux due to burner misadjustment/ misalignment. * Reduced fluid flow (for any reason) can cause DNB (departure from nucleate boiling). Tube rupture occurs quickly after DNB has occurred. Difficult to predict or assess severity API571 (4.2.11)| mh Fe eee ee I FIG B8 f Steam Blanketing DNB I - Departure from Nucleate Boiling - i Steam blanket forms and insulates the tube wall Tube wall Fluid flow restriction ‘Tube overheats, bulges and splits as a short-term | overheating failureSECTION fs: Damage Mechanism Mechanical Metallurgical Degradation (Group 1) K DISSIMILAR WELD METAL (DWM) CRACKING Appearance Cracking of ferritic/austenitic Cracks at weld toes in the HAZ steel dissimilar weld joint due to differential thermal expansion Inspection: Requires 100% VT to check weld bonding on ‘buttering’ weld overlay | 100% PT after weld completion Critical factors: « Common in low-carbon or low-alloy to I austenitic stainless steel welds. | © Worse above 260°C (510°F) ‘Thermal cycling increases the problem | * Carbon diffusion from the weld makes things worse at above 427°C (800°F) for LCS | and 510°C (950°F) for low-alloy steels. | FFP/Severity: Cracking is unpredictable and difficult to assess References: API 571 (4.2.12).‘Quick Guide to Damage and Corrosion Mechanisms — APLS71 FIG B10 | Minimising DMW Cracking in Dissimilar Joints I 300 $5 oF Nealloy Douttered weld layer can help reduce ‘cracking potentialPEAS aR ESE Hes eaaean eval mh ; STRAIN AGEING Description Appearance Loss of material toughness _Brittle cracks on the micro/ due to stresses over time macro scale | __ Inspection: Critical factors: | FFP/Severity: References: Metallographic replica testing to reveal micro- cracking in the metal structure. Surface hardness testing. * Mainly affects older, impure, un-deoxidised low-carbon and C-0.5Mo steels. * Worse in cold-worked material that has had no PWHT. Strain ageing is limited to older steels. Time/ stress cycle exposure will be difficult to determine so damage severity is almost impossible to assess. API571 (4.2.4)mi ea omer eke hr FIG B12 Strain Ageing Expansion/Contraction ‘Thick-walled component under pressure cycles Intermediate temperature 10-250°C WN” Multiple pressure cycles over long + lifetime Old C or C-Mo steel 1930...1940...1950...1960 Material developes micro- cracking * Increased hardness * Reduced ductility * Reduced toughness * Increased brittlenessaE a ae eat pcan gerieariee ree mh CAVITATION Appearance Erosion caused by the collapse _Sharp-edged local grooving or of small vapour bubbles in _ pitting areas of low fluid pressure Inspection: | Critical factors: FFP/Severity: | References: ‘al P Co Rotating components can vibrate badly under cavitation. VT or UT/RT to identify loss of wall thickness (Lown). Occurs on pump impellers/casings, downstream of control valves/orifice plates, heat exchangers and other areas with rapid fluid flow/pressure variations Requires a low-pressure area to occur, e.g. suction side of pump impellers. On rotating components, unbalance/vibration may be more important than LOWT. Strong/hard materials can be more prone to cavitation damage than softer, ductile ones, API 571 (4.2.15). Pitting assessment (from one side of component only) to API 579 (Sec. 6).SECTION C: Damage Mechanisms: Loss of Wall Thickness (LOWT) (Group 2)TE PL Ter mh GROUP 2 DMs LOSS OF WALL THICKNESS (LOWT) - UNIFORM OR LOCALISED — Galvanic corrosion Atmospheric corrosion Corrosion under insulation (CU!) Cooling water corrosion Microbiologically induced corrosion (MIC) Soil corrosion Dealloying Graphitic corrosionGALVANIC CORROSION Description Appearance Corrosion at the junction/HAZ Grooving or pitting corrosion in of dissimilar material structures more anodic material Inspection: VTor UT thickness checking Disassembly of flanges/bolts, mating facesetc. | may be necessary to find galvanic corrosion. Critical factors: A weld in a single material is sufficient to act as a dissimilar metal structure — it doesn’t have to | be two different materials. Buried pipelines or similar components in a I conducting soil ‘electrolyte’ commonly suffer from galvanic corrosion. | Small anodic areas/large cathodic areas cause | ‘the worst corrosion in the anodic areas. FFP/Severity: Corrosion in weld HAZ can lead to stress Il concentration and cracking. \ Dangerous when hidden, e.g. necked bolts inside flanges. | References: API 571 (4.3.1). Local corrosion/grooving or pitting is assessed to API 579 (Sec. 5 and Sec. 6, respectively) ISECTION Danage Neha Low of Wall Tihs LOWD rosp 2 mK ' FIG Cl { LOWT DMs of API 571 -A Workable Breakdown — * Galvanic You can think of these. xtmospherie Subgroup A [li 25 generic corrosion > principles = * Cooling water corrosion. Corrosion found in ——~ * Condensate I Subgroup B MB oier systems * Cp + Flue gas J dewpoint Corrosion found in. ——~ * MIC Subgroup C Mil} tanks and pipework ——- Soi | “+ Caustic Dealloying in — ° Dealloying | Subgroup D HB} seawater systems ——t pegraphistionmw ut. toot ent FIG C3 Galvanic Corrosion — Some Keystone Points - WW the gaivanic series - see API 571 for full ist a ® ES Note that LCS is di 30085. oF is | (ae \ Sens camaccnmn tae crea SORIA in Rt nara | Anodic material corrodes Into HAZ Changed microstructure in HAZ (larger unretined rain) makes it more anode , sot corrodes prelerentialy tothe cathodic parent metal Unafected by the heat and the welder metal * PWHT helps minimise (not prevent) this by refining the microstructuressomone iotnaniansorncnes il | ATMOSPHERIC CORROSION Description Appearance | Corrosion due to moisture in General or localised wall the air Inspection: | Critical factors: | _ FFP/Severity: References: thinning accompanied by scaling (rust) VTor UT thickness checking from uncorroded side UT can be difficult owing to poor probe contact and/or back-wall echoes. See our Corrosion Severity Cards* for severity grades. Worse in marine, chloride-rich environments. Attacks most carbon and low-alloy steels. Corrosion rates increase with temperature up to 121°C (250°F). Above this, surfaces are too dry for moisture-based corrosion except where moisture is trapped under insulation, Usually results in leak-before-break as LOWT can be monitored. Can be protected by suitable coatings. API 571 (4.3.2). General wall thinning assessment to API 579 (Sec. 4). | __*Motthews Taning Corrosion Severity Guide, avelabe free. Contac through our website vrww.matthews-taining.co.uk.mi ‘Quick Gude to Damage and Corresin Mechanisms APIST1 ! | CORROSION UNDER INSULATION (CUD Description Appearance I Corrosion resulting from water Localised wall thinning or trapped under insulation pitting in carbon steels Crevice corrosion/SCC in stainless steels in a chloride environment Inspection: VT (external) after insulation is removed. UT thickness checking from inside insulated vessels. Critical Factors: Can occur in any temperature-range components that are in intermittent service. { Risk range is (12°C) to (+175°C) for low- carbon/low-alloy steels. | Risk range is (60°C) to (+205°C) for austenitic and duplex stainless steels. FFP/Severity: CUlisa very unpredictable DM. { Removing 100% insulation is the only reliable way to find it. Commonly causes localised LOWT in LCS. References: API 571 (4.3.3). Assess localised LOWT to API 579 (Sec. 5). Isecre ene MESES Ts wa SS SS mh I FIG C6 J cul i - Some Key Points - Austenitic/ duplex stainless low-alloy steels Real 10F-350°F C12°C-175" 140°F-400°F arco Pedter as LCS, low-alloy or stainless steel lagged pipework is | vulnerable CUI causes general/local wall loss ‘When temperatures are cyclic/intermittent, all | temperature ranges are at risk The most seve between 212°F ang corrosion occurs 00°F (100°C and 121°C)mi ‘Quick Guide to Damage and Corrosion Mechanisms ~ API 571 COOLING WATER CORROSION Description Appearance Scaling and corrosion inside Wide variety of appearances, LCS systems caused by scaling, pitting, general LOWT dissolved 0,/CO2 gases and salts Inspection: Opening up flanges for VT of pipelvessel internal surfaces. Chemical monitoring of process fluid for corrosive conditions. Critical factors: Scaling/corrosion increases > 60°C (140°F). { Low fluid velocity promotes corrosion. Dissolved 0, and CO; increase corrosion rates dramatically. Corrosion occurs rapidly under scaling. FFP/Severity: Generally causes leak-before-break, particularly in lower temperature systems. Local-v-general LOWT is unpredictable — highly dependent on pipework geometry and flow | patterns. Stainless steels can suffer stress corrosion cracking (SCC) ~ more likely to result in unpredictable cracking failure. References: API 571 (4.3.4) Isxc pa Hsia Lf i on. ee mh | MICROBIOLOGICALLY INDUCED CORROSION (MIC) | Description Appearance Corrosion caused by living Localised cup-shaped pitting | bacteria or algae inside tanks —_ under slimy deposits or and cooling systems tubercles (blisters) Inspection: Foul-smelling deposits. VT of internal surfaces. Monitoring of biocide chemical levels to prevent MIC occurring. | Critical factors: Requires water and stagnantlow-flow conditions to occur. Temperature range —17°C to 113°C (higher for some organisms). Can be treated with biocide chemicals. Hundreds of different microbe types - laboratory analysis required to determine the ! correct biocide chemical prevention. | FFP/Severity: Very unpredictable in severity and extent. Normally results in leaks rather than | catastrophic failure for LCS systems. Likelihood of catastrophic cracking in stainless | steel systems, | References: API571 (4.3.8)mh ee FIG C10 MIC and Soil Corrosion ~Key Points _— ae Mic vadaroets monitors Hydrocarbons, promote MIC range MIC cavities may be ~~“ 0-235 oes we o Pt fomeed MIC likes static/low- no flow conditions External coating is the Dest protection TE A External thinning andjor pittingSECTION C: Damage Mechanisms Loss of Wall Thickness (LOWT) Group 2) mh ; SOIL CORROSION | Description Appearance Corrosion of metals in contact External LOWT with local with soils (tank bases, buried corrosion and/or pitting pipelines etc.) | Inspection: Critical factors: Affects low-carbon steels and cast/ductile irons. | Not particularly temperature-dependent; soil corrosivity isthe main driver. | Stray currents, differential corrosion cells and | MIC make corrosion worse. Cathodic protection (CP) systems reduce corrosion by keeping components cathodic I relative to the surrounding soil. FFP/Severity: General/local wall thinning causes leaks rather | than catastrophic failures. Can still have dangerous consequences in gas pipelines or | tanks containing flammable fluids. | References: API 571 (4.3.9). FFP assessment (general) to API 579 (Secs 4, 5, 6) or ASME B31G/DNV-RP101 for Il pipelines.mh (Quek Gude to Damage and Corrosion Mechanisms ~APLST1 I | DEALLOYING Description Appearance I Corrosion in which selective Visual change. May or may not elements are ‘leached out’ of suffer crumbling or LOWT a metals structure leaving weakening or porous dealloyed structure. Inspection: VT may show dealloying but is not 100% | reliable. Macro/micro metallographic examination is more definitive. I Hardness tests, Dealloyed material generally becomes softer. Critical factors: Typical DMs are dezincification, denickelisation, graphitic corrosion; named after the element that has been removed. | Affects mainly copper alloys (brass, bronze, tin) and cast iron (Cl), e.g. in cast valves and pipe fittings. | Contact with soils, water steam or acids can produce a dealloying environment, depending! on the material. I FFP/Severity: Produces serious weakening. Catastrophic failure likely in advanced cases. | References: API 571 (4.3.11). Difficult to assess to API 579 owing to the serious and unpredictable extent! of weakening. \screws sca Tas Wa asees GTN wm ; GRAPHITIC CORROSION | Description Appearance Dealloying of iron from cast _Visual change (sometimes). iron Softening and crumbling | Inspection: VTor hardness testing of component. I UT is of little use, Metallographic replica testing can confirm the I damage. Critical factors: A specific type of dealloying in cast irons. The iron leaches out, leaving a weak porous | graphite matrix. Affects grey Cl. White Cl is not affected to the | same extent as it contains no free graphite. | FFP/Severity: Causes serious softening and weakening. Catastrophic failure of cast valve bodies and I pipe fittings. References: API'571 (4.3.12). Difficult to assess to API 579 ‘owing to the serious and unpredictable effects | of softening/weakening.mw 088s tennant FIG C13 : Dealloying and Graphitic Corrosion Parts ofthe alloy structure sulfer ran Pealloying pretension Pre Cun De oy Je x lm weak 7 wate’ Tener flow can have an ‘The remaining. t. is weak | flect and porous. ln bras tis the zine that le removed | Graphitic Corrosion ~ Specifically for Cl i Iron Fe) matrix, Graphite remains | Conrodes aay Acide (low pH) I stagnant conditions ™ iSECTION D: Damage Mechanisms: High Temperature (>400°F) (Group 3)SECTION D: Damage Mechanisns: High Temperature 400° (Group mi GROUP 3 DMs HIGH-TEMPERATURE DMs > 400°F Creep rupture High-temperature oxidation High-temperature sulfidation Carburisatior/decarburisation Metal dusting Fuel ash corrosion/slagging High-temperature H/H,S corrosion 475°C (885°F) ferrite embrittlement Temper embrittlement Graphitisation and spheroidisation Sigma phase embrittlement Reheat cracking High-temperature hydrogen attack (HTHA) Nitridingmh (ule Gade to Damage and Corrosion Mechanlans~APL571 I [ FIG D1 f High-Temperature DMs by Temperature ! Contaminants entering the metal ‘900°F-1500°F + About 1000°F + Carbon Teaches out of the metalI SECTION : Damage Mechanisms: High Temperature 400 Group 3) mK I FIG D2 A Set of High-Temperature Cracking DMs i Key Points | gy Velnerabitty: Viral lf meat materiats wit be wutnerabe to these DMs Cracking location: On balance, most of the cracking from these DMs lends up as surface-breaking Physical features: Features such as notches, stress concentration changes of section and physical restraint make these DMs worse. | ‘Thick walls provide an excuse for a crack to startmw aoe areata eee an CREEP RUPTURE l Description Appearance I Deformation under time/ Deformation, leading to | temperature/stresses below the cracking and stress rupture yield stress l . | Inspection: Micrographic replication can detect creep inits | early stages. VT for bulges and deformation in later stages. | VT/PTIUT for creep cracking of welds. | Critical factors: Creep causes low ductility in higher strength material and welds, Weld HAZs are affected worse than parent ' material (see Fig D4). Threshold temperatures for creep vary with | material (see Fig D5). FFP/Severity: Creep has several accepted growth phases: * Initiation | Linear growth * Cracking/failure stage | Prediction is difficult and varies with technical opinion. References: API'571 (4.2.8). FFP assessment to API 579 \ (Sec. 10).SECTION D: Damage Mechanis FIG D4 The Specific Problem of Low Creep Ductility Low creep cluctility s one of the eritical factors affecting a materia’s response tocreep Brittle deformation Us effect age a : 2 AND tisa common cause of reheat J cracking ‘The microstructure shows ‘creep void damage, but there is Tittle evidence of accompanying physical deformation It is caused by: + Temperature and stresses at the lower end of the creep range for the material + A coarse-grained microstructure (big grains) + Carbides in the microstructure (for some Cr-Mo steels) ‘So we can think of low creep ductility as: A MATERIAL PROPERTY.Ki FIG DS \d Corrosion Mechanisms APIS7L Appropriate Threshold Temperatures* for Creep Low-strength LC High-strength LCS; U C-1/2 Mo steel 11/4 Cr-1/2 Mo low-alloy steel 2.1/4 Cr-1 Mo-V low-alloy steel 5 Cr-1/2 Mo alloy steel 9 Cr-1 Mo-V high-alloy steel 12 Cr high-alloy steel 304 stainless steel 316, 321, 347 stainless steels Alloy 800 * Ref API 571 table 43 (2011 edition) www.matthews-trai UTS < 414 MPa (60 ksi) 414 MPa (60 ksi) ng.co.uk 3°C (650°F) 371°C (70°F) 399°C (750°F) 427°C (80°F) AA1°C (825°F) 427°C (80°F) 454°C (850°) 482°C (900°F) 510°C @50°F) 538°C (1000°F) 565°C (1050°F)SS bsp espe oe mh HIGH-TEMPERATURE OXIDATION | Description Appearance A high-temperature scaling’ General LOWT under oxide- corrosion mechanism in plain scaled surface carbon steels, Most common in boilers and fired heaters Inspection: UT to measure LOWT. | Macrograph to measure scale thickness on boiler tube internal surfaces. | Critical factors: Will affect all iron-based materials | Affects LCS at metal temperatures > 538°C (1000°F) and 3165S > 816°C (1500°F) | Requires the presence of oxygen to occur. | FP/Severity: Scaling on tube external surfaces can reduce wall thickness to the point of leaking or | catastrophic failure. Difficult to assess accurately to API 579 owing | to local scale/thinning concentrations. | References: API 571 (4.4.1)KK Rae eee eee rey FIG D7 High-Temperature Oxidation ~ Key Points — Remember: this is the tubes high-temperature sealing Burner type of oxidation 1000°F « Low-carbon steel Les boiler components 1500°F + a aa Carbon steel degrades to oxide scale at high temperature Resistance is improved by increased chromium content High resistance 1800°F 30085 ‘ scr Ter er wer Lcs Low resistance y 1000°Fcei geen norma Lary Beas mh | HIGH-TEMPERATURE SULFIDATION Description Appearance | Corrosion of LCS and other Serious, normally uniform, steels caused by contact with LOWT sulfur compounds > 260°C (500°F) Inspection: UT thickness measurements or profile RT. PMI to confirm material vulnerability to sulfidation (McConomy curves) Critical factors: Chromium content provides protection against | sulfidation. H2S (sour) systems are commonly affected. | Sulfide scaling on the component's surface can | offer a (temporary) degree of protection. FFP/Severity: _ Sulfidation is a common and catastrophic DM in | refineries. Serious LOWT results in principal stress failure (split) of pipework and tubes. | Corrosion rate can be non-linear and non- uniform, so is difficult to predict accurately. | Assessments to API 579 can be inaccurate. | References: API 571 (4.4.2)K {4 donde tic FIG D9 High-Temperature Sulfidation ~ Key Points - This centres around the ‘McConomy’ corrosion curves Mecomomy slidation Corrosion mkipter curve ence 1.6% S content , 100+ ee ib so coneson | e380 eng \ & ip 10 - %s ' | On On ! I ' 7 ; 1 i sob solr ch yoo Corrosion rate multiplier { ‘Temperature Suifidation is a wallthinning ‘corrosion DM. | Threshold temperature 50°F 260°C) ~ ur \ checks for | thinning‘SECTION D: Damage Mechanlsms: High Temperat conemes Description CARBURISATION/DECARBURISATION Appearance | Carburisation is where carbon Carburisation causes surface is absorbed into.amaterial embrittlement and cracking structure. Decarburisation is Decarburisation causes ‘the opposite—carbon leaches weakening, leading to stress out, leaving an iron-matrix. failure Both are high-temperature DMs | Inspection: | Critical factors: FFP/Severity: References: Metallographic (rej ination can confirm the extent of both carburisation and decarburisation. Carburisation: VT for flaking or spalling of the surface. Carburisation requires high temperature > 593°C (1100°F) and the presence of a carbon- rich material. Both cause lack of ductility and weldability. These are unpredictable DMs which are not easily assessed. Both carry a risk of catastrophic failure API 571 (4.4.3, 4.4.4). API RP 941 Steels in High Temperature Hydrogen Environments.K Fee ees ee eT METAL DUSTING Description Appearance An extreme form of Most commonly pitting, filled carburisation occurring ina _with flaking metal dust and CH-stream process carbide deposits environment Critical factors: FFP/Severity: References: UT thickness checking or VT of affected surface. Profile RT of small-bore pipework. Metallographic tests to show the degree of carburisation under an attacked surface. All metal alloys can be affected by metal dusting under the necessary process conditions. Attack can be more localised in stainless steels. Highly dependent on the precise composition of the CH process stream. Can cause catastrophic failure so FFP assessment is not practical, once identifiable metal dusting is discovered, API571 (4.4.5).SECTION Ds Damage Mechanisms: High Temperature 400° (Group 3) mh FIG D11 Four Related High-Temperature Diffusion DMs Carbon diffuses to the surface and leaches out Fe (ron is left) f Decarburisation Carbonich gas stream ‘Low-carbon’ festa —— Hittemp 1100°F +| Carburisation ‘Carbon deposits to the surface and then CC eaehes in Reducing sas [00rF-T500 7 rear ernie ore (ciech, oreo) aie Ammon Free sot and ibe Nstere! rape dint Scessive Cprespation and dlusion into the surtace Cross-section of affected metal Graphite © ust CARBURISING [METAL DUSTING] Har, bite layer : artage apts DECAREDRENG fe rte layer for S$ RITRIDING Weakened layer gf Fark grey surtace layer with carbide lost (and increased hardness)mh sso angel Sores cae iar | FUEL ASH CORROSION/SLAGGING Description Appearance Corrosion under gas-side ash Slagging and severe metal loss slag deposits on boiler and (up to 1 mm per year) fired heater tubes a Cm Inspection: _ Visual inspection on the gas side of fired tubes. UT measurement of LOWT after removing slag by grit-blasting. | Laboratory analysis of slag deposits. Highly dependent on slag melting point in the coal or residual oil fuels. Oil ash contains vanadium pentoxide and sodium oxide/sulfate. Melting points > 538°C | (10°F). | Coal ash contains sodium and potassium iron trisulfates (NaSO3, KSO3) with melting points | between 544°C (1030°F) and 610°C (1130°F). FFP/Severity: Severe metal loss causes catastrophic failure of boiler tubes. These are inside the boiler so | rarely present an external risk. LOWT is uneven and unpredictable so FFP | assessment is rarely practical. | References: API571 (4.4.6).sxc np Mc mS EN mh : FIG D13 : Fired Boiler Showing Slagging/Corrosion Zones Zone (I): Furnace waterwall See Fig DIA Zone @): Superheater/reheater tube for slagging details Zone @): Economiser ® ag Boller casing Superheater ‘ef and reheater tube banks Boiler furnace “waterwall tubes Powdered | coal 1 A 1 | Slag contaminants > come from the a | fuel source Ges mm) Cleon fw contaminant level | O11 mp Vanadium pentoxide (VO soa Coat mh Sodium and potessu trvalaesri (Quick Guide to Damage and Corrosion Mechanisms ~ APISTI FIG D14 Key Points about Fuel Ash Slagging Zone (1): Furnace/waterwall slagging Clreumferential grooving left underneath Waterwall tube Temperature cycling causes ‘00°F start Ne) nerinal fatigue 1000°F worse Slag falls off ‘Uncooted supports will be at higher temperature Zone @): Superheater/reneater slagging All sag causes corrosion ——o| Otkash corrosion: by the formation of iron MF sreyiblack qui! slag oxide underneath it on surface, grooving Gas underneath: ~ Coal-ash produces less or no grooving under the slag deposit General - the formation of slag Fossil fuel is contaminated with: sal A high temperature + Potaston 9 TRoewomes pe soles to + Vanadium (V) + Sout gw) eeATED Pap isn tp a OT mh HIGH-TEMPERATURE H2/H2S CORROSION Des Appearance Ahigh-temperature Heavy grey scaling (iron sulfide) sulfidation-type DM made covering LOWT. worse by the presence of Ho in HAS (sour) process streams) Inspection: Critical factors: | _ FeP/Severity: VT, UT or RT to monitor LOWT. Threshold temperature > 260°C (500°F) as for sulfidation. Corrosion rates can exceed those for straightforward sulfidation. Chromium content > 7% starts to improve resistance. 300 series stainless steels should be highly resistant within their prescribed service ‘temperatures. The scale can be tightly adhered, so should be removed by grit-blasting before measuring accurate LOWT. LOWT can vary on tube bends, fittings etc., so accurate FFP assessment is difficult. Catastrophic failure risk can rarely be eliminated. API571 (5.1.1.5)‘Quick Guide to Damage and Corrosion Mechanisms~ API 571 FIG D17 A Quick Guide to Embrittlement | The key differentiating point Is the material that is ‘Temper embrittlement vulnerable to the DMs Lowalloy steels (eg. 24Cr-1Mo) 650°F-1070°F| Strain aging Vintage low-carbon steels and | + Loss of €-0.5Mo. Temperature not that toughness/ductility important + Increase in hardness + Intergranular eracking | * Brittle behaviour 885°F embrittlement The results are similar Ferrite-containing 400 Ss/Duplex SS I between types = risk of '885°F-1000°F, but can occur slowly brite fracture, mainly during from 700°F upwards | start-up, when temperatures are lower Embrittlement causes: ‘Sigma-phase embrittlement ‘300 $8 and castings with ferrite ‘+ 400 series with ferrite + Duplex $8 with ferrite 1000°F=1700"F Brittleness of new materials Is a different issue — caused by combinations of: ‘+ Embrittlement phases formed during steel manufacture | + High carbon content ‘+ Thick wall section(s) | ‘+ Temperatures (normally during hydrotest) below the ductile-to-brittle transition temperature |s#cron ees deine tna Teenlin en ones wm 475°C (885°F) FERRITE EMBRITTLEMENT Description Appearance High-temperature Found by increase in hardness/ metallurgical change causing —_ decrease in Charpy impact loss of toughness in alloys strength. containing ferrite Possible visible cracking in its later stages Inspection: Surface hardness test (Vickers, Brinel, Rockwell), Charpy/lzod impact test. Weld bend test. VT for cracking during shutdown. Critical factors: Only affects ferrite-containing alloys, such as 400 series (405, 409, 410, 430, 446) stainless steels and duplex stainless steels (e.g. alloys 2205, 2304, 2507). DM temperature range >475°C (885°F), hence its name. FFP/Severity: Brittle fracture risk at start-up (cold) conditions. Limited assessment is possible using API 579 (Sec. 9, cracking) but accuracy will be limited. Note: This DM cannot be reliably detected using metallographic replication. References: API 571 (4.2.5)| mi Rie pee aoe neem th | FIG D19 885°F Embrittlement Increase in hardness / \—=— Ferritecontaining Brittle inter-metallic ‘precipitate’ stainless/duplex: phase increases with time, causing I microstructure significant reduction in toughness (increase in brittleness). | NOTE: 85°F embrittlement is reversible using heat treatment at typically ! 599°C (1100°F) followed by rapid cooling. Practically this can be dificult to i achieve | Followed by cracking (under cold start-up conditions) ae SCC occurs | (none form or So another) | ‘The material fails by (cack ropsgation crack | in preference to (ductile racks are plastie deformation surfacedbreaking | and intergranular (and therefore | branching) So are part of the same story E. Touibsires I Generally residual)GRAPHITISATION AND SPHEROIDISATION Description Appearance Graphitisation is Microstructural changes decomposition of a steel’s involving the distribution and carbon content into graphite form of carbon compounds Spheroidisation is a softening of carbon and low-alloy steels due to dispersal carbides agglommerating into spheres | Inspection: —_VTwill not reliably show these DMs. Metallographic (replica) examination. Tensile test | to show reduced strength/increased ductility. Critical factors: Graphitisation affects LCS and 0.5Mo steels after long-term exposure to 427-593°C (800-1 100°F). | Spheroidisation affects LCS and a wider range of low-alloy steels above 454°C (850°F). | FFP/Severity: Weakening causes principal stress failure (e.g. tensile overload) similar to loss of creep strength. Graphitisation has several forms (random-v- | concentrated graphite nodules) and FFP assessment is unreliable. Spheroidisation softening can cause | unpredictable deformation and bulging —again FFP assessment is likely to be inaccurate, leaving a | risk of unexpected catastrophic failure. | References: API571 (4.2.1-4.2.2)sms ~ APLS7E mi cet ara incl FIG D23 Graphitisation and Spheroidisation ‘These are both essentially Weakening / Softening of the microstructure idl nm jg Spheroidisation ge SS font ¢ netlogeaiic tests Low-carbon or 0.5Mo steel Low-carbon and low-alloy steels up to 9Cr-1Mo Carbides turn into weak graphitic nodules * Ductility increases + Ductilty decreases Carbides remain as carbides but agglomerate into spheres, ‘Temperature sensitivity 1025°F Below 1025°F Above 1025°F Graphitisation ‘Spheroidisation happens first happens firstscmanmtiaiammncininns ly SIGMA PHASE EMBRITTLEMENT Description Appearance Loss of fracture toughness in metallurgical embrittlement stainless steels after high- only confirmed by temperature exposure metallographic and impact test Inspection: Critical factors: FFP/Severity: References: Not detectable using visual examination (VT). Metallurgical (replication) tests of the microstructure. Charpy impact testing of test specimens. Affects stainless steel with high ferrite content (300 and 400 series). Cast austenitic (300) grades are most susceptible. The brittle intergranular ‘sigma phase’ occurs at temperatures 538-927°C (1000-1700'F). The material becomes harder and more brittle. FFP assessment is very difficult as the decrease in ductility and increase in brittleness is variable and unpredictable. Metallographic replicas are open to different technical interpretations. ‘APIS71 (4.2.6) API RP 581 Risk Based Inspectionmw Cee een REHEAT CRACKING Description Appearance Cracking of low-alloy steels Intergranular cracking in HAZ of due to stress relaxation either welds ~ normally surface- during PWHT or high- breaking temperature operation Inspection: MT/PT/UT for surface breaking cracks, TOFD for 23Cr-1Mo-¥, with comparison block. | Critical factors: Most common in thick-walled section owing to 30 stresses during manufacture. Affects low-alloy Cr-Mo-V, 300 series SSand | some nickel alloys. ‘Small cracks act as fatigue crack initiators. FrP/Severity: Can be unpredictable owing to temperature variation during PWHT giving varied risk of reheat cracking. | APIS79 (Sec. 5, Level 2) canbe used; in theory, Can be unreliable due to imperfect data, leaving a risk of unexpected catastrophic | failure. References: API 571 (4.2.19). | {SECTION D: Damage Mechanisms: High Temperature (100° (Group 3) mi | HIGH-TEMPERATURE HYDROGEN ATTACK (HTHA) Description Appearance Exposure to hydrogen at Surface decarburisation plus elevated temperatures causes _ internal methane formation methane (CH,) formation at and cracking. Can occur in grain boundaries, resulting in _ parent material or welds weakening and cracking Inspection: | Critical factors: | FFP/Severity: References: Scanning electron microscope (SEM). Advanced metallographic tests. Surface NDE (PT, MT) in very advanced stages of degradation. Common in high-temperature boiler tubes. Will attack most carbon and low-alloy steels up to 5Cr-0.5Mo, 300 series $5 is not susceptible. The Nelson curves (see AP! 571) show the effects of temperature, time and hydrogen partial pressure on the risk of HTHA. FFP assessment is very risky, once HTHA is established. Boiler tubes suffer catastrophic failure (split or “window flap’ failure) without warning. API571 (5.1.3.10) API RP 941mi Gels ered recess FIG D27 The Mechanics of HTHA l+G=CH, Methane (CH,) builds up pressure, opening cracks Carbides are lost, causing ‘weakening Original grain Decarburised grain structure structureSECTION : Damage Mechanams High Temperature 64007 Group 3) mK NITRIDING Description Appearance Formation of ahard, brittle Little visible change except surface layer or various steels. under microscope after exposure to high- temperature process streams paw ee containing nitrogen Inspection: Visual inspection of surface (may change toa grey colour). Surface hardness testing (> 400HB can indicate | problems). Metallographic (replica) tests and for confirmation of nitrided extent and depth. | Critical factors: Affects LCS, alloy steels and 300/400 series stainless steels. I Starts at temperatures > 316°C (600°F) and gets much worse > 482°C (90°F). Confined to the surface layers of components in a nitrogen-rich process atmosphere (methane reformers, olefin and ammonia plants). Nitriding at grain boundaries > 410°C (770°F) produces quicker embrittlement and micro- cracking. FFP/Severity: _ Embrittlement/cracking is very difficult to ’ predict so FFP assessment is unreliable. Always a risk of unexpected cracking and | catastrophic failure ~ particularly under cyclic (fatigue) conditions. | References: API571 (4.4.7)SECTION E: Damage Mechanisms: Environmentally Assisted Cracking (EAC) (Group 4) ‘www.matthews-training.co.ukscrovcnmetnintnma tenascin GROUP 4 DMs ENVIRONMENTALLY ASSISTED CRACKING (EAC) DMs Chloride sc Corrosion fatigue Caustic SCC (embrittlement) Polythionic acid SCC (PASC) Wet H2S DMs * Hydrogen blistering * Hydrogen-induced cracking (HIC) * Stress oriented hydrogen-induced cracking (SOHIC) * Sulfide stress cracking (SSC) «HF stress cracking + Carbonate alkaline stress corrosion cracking (ACSCC) Ammonic SCC Liquid metal embrittlement (LME)mw cao maura pas cA AM | ENVIRONMENTALLY INDUCED CRACKING (EAC) Environmentally induced cracking (EAC) is a term used mainly by API documents to encompass a set of DMs that involve crack propagation initiated (and encouraged) by process chemicals on a susceptible material. The term environment therefore refers to the process environment inside the vessel or pipework system rather than anything to do with the atmospheric conditions outside it, There are many types and sub-types of EAC, some of which are found mainly in the downstream refining industries, due to the combinations of process chemicals and construction materials | used, Common features of EAC DMs are listed below. | The environment pH is a governing factor high-pH (alkaline) and low-pH (acidic) process conditions encourage EAC in many forms. I Material microstructure is a key factor in the susceptibility of ferrous (and some non-ferrous) materials to EAC. Austenitic | stainless steels are particularly susceptible. | ‘© Welding increases susceptibility to most EAC DMs. High heat input changes a metals microstructure to make it more sus- | ceptible. Conversely, milder heat treatment can actually in- crease the EAC resistance of some low-carbon steels in sour (H2S) service. | The scope of EAC | The four figures E1 to E4 show some of the main features of EAC. Fig £1 shows the overall picture for SCC of steel (perhaps the |SECTION E: Damage Mechantms: Environmentally Aslsted Cracking (EAQ (Group 4) nm most common form of EAC) and its links with other embrittle- ment DMs. Note the prevalence of sour (H2S) and alkaline (caustic) process conditions. Fig E2 shows the influence of welds on the expected appearance and location of EAC DMs. Weld heat-affected zones (HAZs) can be host to several different cracking forms, particularly if PWHT has not been carried out. Fig £3 shows how both high- and low-pH process conditions can encourage different forms of EAC. All get worse, the further the pH deviates from the pH 7 (neutral) state. Finally, Fig E4 shows the wide spread of steel alloys that can be affected by EAC DMs. Corrosion-resistant elements such as chro- mium and nickel can actually increase susceptibility to EAC when added in certain percentages. To complicate matters, the issues shown in Figs E1 to E4 all act together to cumulatively influence whether a particular material/process combination will be at risk of being affected by EAC. It is always a complex picture.mw Rene eee cee eee FIG El Environment-Assisted Cracking DMs ~ The Overall Picture — Chloride scc Poiythionie SCC (PASC) Fihanol Huld Sc Carbonate SCC Amine Alkaline SCC Sulfide SCC scc r (rom Hs) ; Caustic i sce . ea Lgaid metal embriteren : eo (LM) ® eseomimon zl usc Hydrogen embritilement For non-ferrous Cu alloys “Ammonia CulNi/Zn Sulfate scc a alloys a secsermon mt mtn FIG E2 Environment-Assisted Cracking — By Appearance and Location - + Chloride sce ‘+ Hydrogen stress cracking Cracking is * 'Spider-like” “Brin svomgetenng Hegel ane + Intergranular lydrogen blistering (HAZ) + Surlace-breaking Carbonate cracking can be turther away from the = weld (step-wise Cracking is: cracking) + Caustic SCC + HAZ of non-PWHT'd welds * Polythionie aeia SCC Parallel to the weld (pasce) * Surface-breaking * Amine sce ‘ Intergranlar + Carbonate SC # Straight of branching * sorte + Sulfide (HS) stress crackingmw sb ened foi tier FIG E3 Environment-Assisted Cracking ~ By pH Environment - This fig shows the broad pH influence of SCC mechanisms (as mentioned in the descriptions in API 571) pH 12: Alkaline/Caustic Caustic Ammonia ieee \ sec / \ / L \ AN 8 we ' i a tis, j =i 5 i \ / \ / VV nae A mst ones ‘Note: SCC mechanisms not shown here may be affected by pH — but it is not identified in API571 as a major ‘driver2S Sg nao Seen and Sing EO Kav KK FIG E4 Environment-Assisted Cracking ~ By Material Susceptibility — ‘Treat this fig as guidance only — read in conjunction with Fig ES DUPLEX 00 Increasing Creontent — AUSTENITIC STAINLESS STEEL 300 carson tee. | LOW-ALLOY STEEL Annona SCC Poyionie SCC Banal foal SCC Chiorde SCE “nine SOC Carbonate (alkaline) SCC Hy exacking af high-strength steel Wet iS damage (HIC) Caustic SCC (45.3) hydrogen embritiementmw eae peter reeset He CHLORIDE SCC I Description Appearance | Environmental surface Surface breaking fine multi- ! cracking of 300 seriesSS and branched cracking some Ni-based alloys caused by stress and an aqueous chloride (Cl) process environment Inspection: Visual examination for cracking (abrade surface | first to remove oxide film). PT or ECT are the best methods. I RT will rarely find SCC as the cracks are too fine. Critical factors: Worse under wet lagging or in crevices. Residual welding stresses (or cold-forming | stresses (e.g. bellows)) are generally more responsible for SCC than principal (pressure) | stresses. I SCCis not particularly temperature sensitive; however, it gets worse at temperatures > 60°C | (140°F). FFP/Severity: Can (in theory) be assessed to API579 (Sec.9), | but results can be dangerously inaccurate. Not | recommended Chloride SCC is one of the most common causes | of catastrophic cracking failure of 304/316 SS I components. References: API 571 (4.5.1) |SECTION E: Damage Mechanlams: Environmentally Assisted Cracking EAQ (Group KK CORROSION FATIGUE Description Appearance Cracking failure due to an Initial cracking with little plastic environmental corrosion deformation mechanism being combined with cyclic fatigue Inspection: PT/MIT/UT for crack detection. Cracks can be tight and difficult to detect in their early stages, Critical factors: Common in boiler tubes, deaerators and stays! structural attachments. Fatigue cycling will exaggerate the effects of any EAC damage mechanisms. There is no stress (endurance) limit below which fatigue will have no effect owing to the of the corrosion mechanism and iators. FFP/Severity: Most FFP assessments are invalidated by th existence of the cyclic ‘crack growth’ condition. Combined mechanical (vibration) and thermal stresses present the highest risk. Catastrophic failure is commonplace, and so always a risk References: API 571 (4.5.2)mK (Ga cdchasraieraaiaees eet CAUSTIC SCC (EMBRITTLEMENT) Description Appearance A type of SCC caused by Fine cracking parallel to the exposure to caustic (highly weld, in HAZ parent or weld alkaline) process fluids metal Pe Inspection: Surface crack detection using VI/PTWEMT following grit blasting. { RT has limited ability to find fine cracks. Critical factors: Frequently occurs adjacent to non-PWHT'd | welds. | Main causes are > 50 ppm concentration caustic soda, sodium hydroxide (NaOH) and caustic | potash (potassium hydroxide (KOH). Risk of failure during steam-cleaning of LCS components in caustic service \ FFP/Severity: Severity increases dramatically with temperature (unlike other types of SCC). I PWHT of welds can reduce the chance of caustic | cracking FFP assessment to API 579is unreliable owing to. | unpredictable degree of embrittlement. References: _API571 (4.5.3), NACE SP0403 Avoiding Caustic | SCC of LCS Refinery Equipment and Piping. |rer nesgies cae ese any tds GELS pee wm POLYTHIONIC ACID STRESS CORROSION CRACKING (PASCC) Description Appearance A type of SCC of stainless steels Localised cracking in or near caused by sulfur-based acid welds Inspection: Critical factors: | FFP/Severity: PT for surface breaking cracks (abrade/ flapwheel the surface first to remove oxide scale). Cracking may occur during shutdown periods, so time inspections accordingly. Residual stresses from welding are sufficient to cause PASCC. Affects sensitised (300 series) austenitic stainless steels, i.e. that have chromium carbides formed at grain boundaries due to temperature exposure at 400-815°C (750-1500°F), either during manufacture, PWHT or process service. Sulfur-containing environments occur in fired units, FCC units, hydro processes, etc. Flushing (and possibly descaling) to remove acidmi (GL gen Earnie deposits is necessary to stop further deterioration. Cracking can be unpredictable and progressive, so FFP assessment to API 579s unreliable and always carrying the risk of unpredicted catastrophic failure. Sensitisation in 300 stainless steels can sometimes be reduced by heat treatment. Specialised advice required. References: P1571 (5.1.2.1). See also amine SCC as a similar DM. API 571 (5. 2) NACE RP 0170. Protection of Austenitic Stainless Steels from PASCC.error vanes Benatar tieeedy) RECTUSEg eG ee wm I FIG E8 - Caustic Service Risk Graph* for Low-Carbon Steel — ALLOYS rf On Nay i Lend CAUSTIC us + | 100 | ‘Temp °C | 15 | | 50 | | LOW RISK OF CAUSTIC 2 EMBRITTLEMENT/CRACKING | -No PWHT necessary ~ 10% 20% 30% 40% 50% % Concentration sodium hydroxide (NaOH) * Acknowledgement: API571 (Fig 4146)i KK OO caer apaneren ree aces WET H2S DAMAGE MECHANISMS (SET OF FOUR) | Description Appearance There are four main DMs These are all cracking DMs associated with wet sour process streams: * Hydrogen blistering * Hydrogen-induced cracking (HIE) «Stress oriented HIC (SOHIC) * Sulfide stress cracking (SSC) Inspection: Surface crack-detection techniques PT/MT/VT. Critical factors: All these DMs are related to the permeation of | hydrogen through steels. Factors include: * HDS partial pressure * Temperature | © Material surface hardness * Existing material laminations and defects causing localised stresses. | FFP/Severity: These DMs may act singly or in combination, making accurate FFP assessment very difficult. | API579 can be used to assess hydrogen blistering, but accurate input data are required. Cracking DMs are difficult to assess accurately. | There will always be a risk of unexpected catastrophic failure. | References: API571 (5.1.2.3). NACE RP0296 Guidelines for Cracking of Vessels in Wet HS Environments. | NACE 8X194 HIC Resistant Steels.SECTION: Damage Mechanin: Environmentally Asated Cracking (EAC) Group 4) K FIG Ell The Hydrogen-Based DMs of API 571 - A Summary - Hydrogen embrittlement (HE) _——— en —— ‘An embrittlement DM ALOWT DM _ A result of methane (CH) pressure/permeation coupled with decarburisation —-—. ~N Z ‘Wet HyS damage set High-temperature + Blistering pyeimncentatineks *HIC + SOHIC oe ——— Aresuit of the Hy molecule ‘AH, alfusion and embrittlement presence and permeation Datmw (ule Gade to Damage and Caresion Mechanisms APISTI I FIG E12 I Wet HS DMs ~ The Set of Four - I SSC: Sullate stress cracking SOHIC:.Stress-created hydrogen [Wer Hs Das} induced eracking f Hic: Hydrogen induced eracking Hy blisters] | Hic SOHIC ssc and they are all influenced by — pH ¢H,Sconcentration + Temperature * Hardness | ‘Steelmaking ‘quality’ « PWHT wert envroamen A ff ee Corrosion under scale (sulfide corrosion) produces Hy, Hydrogen blister Scale ssc cracking | tinder tae pn ae Teal hard | area helps ' cracks to Hydroge SOHIC at weld — Mae I blister stepwise stacked cracks soyuc ata ss¢ erace weld Gevbsurace) cracking, can penetrate and HAZ, SOHIC is generallyin | the parent metalSECTION E: Damage Mechanisms Environmentally Assisted Cracking (EAC) (Group 4) mK | HYDROGEN-INDUCED CRACKING (HIC) | Description Appearance Hydrogen permeation into Interconnecting or ‘stepwise’ | grain boundaries/ cracking | discontinuities’ inclusions assists stress cracking Inspection: Surface cracks detection PT/MT/UT. | Critical factors: Can occur between ambient and 150°C (300°F) | or higher. Starts from local grain boundaries/ | discontinuitiesfinclusions. FFP/Severity: _ HIC cracks propagate easily and unpredictably, particularly in a cyclic (fatigue) stress situation. | FFP assessment is difficult — always a risk of crack propagation and catastrophic failure. | References: NACE 8X194 HIC Resistant Steels. API 571 (5.1.2.3). See also API 571 (4.5.6), Hydrogen embrittlement (HE) asa similar | damage mechanism.K (ule Get Damage and Coroson Mechanisms P1371 I | STRESS ORIENTED HYDROGEN-INDUCED CRACKING (SOHIC) ! Description Appearance Asimilar cracking mechanism Perpendicular, through- | to HIC but driven by local thickness stacked cracks in base stresses rather than hydrogen metal adjacent to weld HAZs permeation | Surface crack detection PT/(WFMT. | UT for through-thickness SOHIC cracking. Critical factors: Driven by local stresses (residual or applied). Generally associated with welds, but can also | happen in combination with other wet HS DMs, FFP/Severity: SOHIC is a more damaging form of HIC, | Severity can be reduced by PWHT. Cracking can be rapid so FFP assessment is I unreliable - there will always be a risk of crack propagation leading to catastrophic failure. References: P| 571 (5.1.2.3) I Inspection:SUCTION amg cnt Penney el Cig CAD ae 9 mw | SULFIDE STRESS CRACKING (SSC) Description Appearance | Atype of hydrogen cracking Fine cracking in welds or parent under the influence of wet HS material and tensile stress Inspection: Critical factors: FFP/Severity: References: Surface crack detection PTWFMT/VT, Attracted to areas of local high hardness > 200HB in weld metal and HAZs. A particular danger in high-strength (tensile) steels. Preheat and PWHT can reduce the occurrence of SSC. SSC generally occurs < 82°C (180°F). Very difficult to predict with H2S partial pressures > 0.3 kPa (0.05 psi). FFP assessment unreliable owing to unpredictable local hardness and 3D stress directions around welds. API 571 (5.1.2.3) NACE MR0103 Materials Resistant to SSC in Corrosive Refinery Service. NACE RP0472 Controlling In-service Cracking of LCS Weldments in Corrosive Environments.Ki (ule Gude o Damage and Corrosion Mechanisms ~APIST1 I | HYDROGEN (HF) STRESS CRACKING I Description Appearance A form of environmental Fine surface-breaking cracking cracking in an aqueous HF acid in or near welds environment a I Inspection: Metallographic (replication) test required to detect these fine cracks. Critical factors: Caused by hydrogen permeation generated by the HF environment (similar mechanism to | sulfide SCC), Prevalent in LCS weldments with surface | hardness values > 200HB. LCS with carbon equivalent (CEQ) > 0.43 are | particularly susceptible to HF cracking, | FFP/Severity: Cracking is unpredictable and may be progressive or catastrophic, so accurate FFP I assessment is difficult. Prevention is a better solution than assessment for this DM. Protecting the surface from I hydrogen permeation and limiting carbon contentsurface hardness are well-proven | methods. \ References: API571 (5.1.2.4) NACE SPO472 |SEW mg hsm ted cing TA Goer KK | CARBONATE ALKALINE STRESS CORROSION CRACKING (ACSCC) Description Appearance A form of SCC caused by stress Parallel or ‘spider's web’ and alkaline (carbonate) surface-breaking cracks within process conditions 50 mm (2 in) of a weld | Inspection: Critical factors: FFP/Severity: | References: Monitoring of process fluid for alkaline (pH 8-10) conditions. High-alkaline (pH 8-10) conditions are the driving force. 300 series SS cladding or special materials such as alloy 400 can be used to shield LCS from contact with a damaging alkaline environment. Parallel cracks can be assessed to API 579 (Sec. 9); however, propagation characteristics are difficult to predict for these cracks in the HAZ. Cold-working or mechanical fatigue conditions can make FFP assessments inaccurate. Always a risk of unpredictable catastrophic failure. API 571 (5.1.2.5)mw eee FIG E18 Alkaline Carbonate Stress Corrosion Cracking (acscc) Alkaline (sour) water phase (pH 8-10) Carbonate fons > 100 ppm oo ° Residual stresses eo) trom welding ° Common paratlel Note: ACSCC cracks occur croc boeanans further from the weld than for SSC or SOHIC Te eee es Cracks have spider's web cracking appearanceSECTION E Daeg Heskalos: Enronmerialy Ate Creag GAD Crew 9 mh AMMONIA SCC OF COPPER ALLOYS Description Appearance SCC of Cu-Zn alloy heat Single or branched cracks on exchanger tubes Inspection: Critical factors: FFP/Severity: References: exchanger tubes ECT of heat exchanger tubes (‘Iris testing’). Visual examination of tube external surfaces (difficult for internal surfaces), Lighted borescopes can assist. Monitor pH values in service to give an indication of susceptibility. Occurs under alkaline conditions pH > 8 at any temperature. Low Zn content (< 15%) of Cu-Zn alloys are susceptible. 90-10Cu Ni, 70-30Cu Ni and 300 series SS are highly resistant. Can also affect LCS, but is effectively prevented by using low-strength steels and PWHT. Heat exchanger tubing cracking very difficult to assess using AP! 579 FFP techniques. Tube expanded areas near tubeplate can suffer the worst problem. Will often leak before it is detected. API571 (4.5.4)Gulde to Damage and Corrosion Mechanisms ~ APIST1 mK LIQUID METAL EMBRITTLEMENT (LME) Description Appearance Cracking caused when certain _Localised brittle intergranular molten metals come into cracks in a previously ductile contact with specific alloys material Inspection: Hardness testing and surface crack detection (PT/MT) where molten metal contact has occurred. RT for mercury (Hg) contamination in heat exchanger tubes. Critical factors: Most frequent cause is molten metal dripping ‘onto a susceptible alloy during a fire. New small amounts of molten metal are sufficient to cause LME. FFP/Severity: Cracking can be extremely rapid, instantaneous or delayed, making meaningful FFP assessment next to impossible. Cracks cannot be ground out. Always a risk of unpredictable catastrophic cracking failure. References: API571 (4.5.5) ASM Metals handbook Failure Analysis and Prevention: Volume Iom mai ion FIG E20(b) Liquid Metal Embrittlement (LME) Plant fire causes dripping liquid metal from galvanising, electrical components, copper components, soldering and brazing i I | Cadmium (Cd) Zine (Zn) Mercury (Hg) | Lead (Pb) | | Highstrength 300 series Copper. Aluminium Alloy steels steel alloys alloys 400 I (Tensile >70 ksi)SECTION F: Damage Mechanisms: Refinery Chemical Acid/ Alkaline LOWT (Group 5)iscrum ig: chr ry ems Sin OF KK GROUP 5 DMs | REFINERY CHEMICAL ACID/ALKALINE LOWT DMs Caustic corrosion Boiler condensate/CO> corrosion Flue gas dewpoint corrosion * Amine corrosion ‘www.matthews-training.co.uk 121\de to Damage and Corrosion Mechanisms ~ APIST1 REFINERY-SPECIFIC LOWT DAMAGE MECHANISMS Refinery-specific DMs are a category created by API 571 (Sec. 5.1.1) for convenience. Broadly they encompass a set of DMs that result in general corrosion leading to LOWT, rather than embrit- tlement and crack propagation in refinery equipment. They are predominately caused by acidic or alkaline process environments attacking materials with low resistance. In practice these DMs are found in other process and petrochem- ical plants, not just refineries. Common items such as boilers and fired heaters suffer from some of the DMs in this category. The API 571 classification does, however, provide a useful reference list. Note that only the most common of this DM group are covered in this guide. See API 571 for the full list. 12 ‘www.matthews-training.co.uke z z z 5 Eg SECTION: Dang Mecham Refinery Chenille LOWT reap 5) K FIG Fl Refinery-Specific LOWT Corrosion DMs CORROSION TYPE Amine } rcs Akaline sour water ‘Ammonium chioride! HClacid Hitemp Hy/HS HF acia Naphthenic acid ) (0) Acidic Phenol carbolic acid Phosphoric acid ‘Sour water: acidic 1,504 acid ‘Aqueous organic acid) ©) (©) = Organte acid NOTE SOME KEY POINTS ABOUT THIS 12-DM SET ‘They are mainly the result of process chemicals used in refinery equipment ‘They are generally more complex than the general LOWT DMs in APL571 A lot of them involve various types of acidic salts as a cause of ‘The actual DM: loss of wall thickness (LOWT) is much the same in all of them ‘www-matthews-training.co.ukc 123mi ood caer pane ees weaieees ohn FIG F2 Critical Factors Affecting Acidic Corrosion “Temperature Velocity Actdlc corrosion is generally fairly uniform in nature causing loss of wall thickness (LOWT). It can be worse when located under scale deposis. 124 wwww.matthews-training.co.ukEe eee eee ate eae nee ar mK The key facts about acid corrosion Of the twelve LOWT DMs explained in API 571 (Sec. 5.1.1) all but one involve some type of corrosion by acid. Chemicals containing acid compounds are used in many applications in the oil refining process. They may be weak, or strong, organic or inorganic acids that, given the chance, like to corrode ferrous metals with which they come into contact. What exactly is acid anyway? Anything with a pH level of below a neutral 7 (i.e. pH 1-6) is defined as an acid. The lower the pH, the more acidic it is. Like all chemical compounds, acids are classified as either organic or inorganic. * Organic acids contain carbon, hydrogen and at least one other element. The carbon and hydrogen are held together by so-called ‘covalent’ bonds, which are quite weak, com- pared to other types. You can think of them as natural substances such as naphthenic acid, acetic acid (vinegar), citric acid (fruit juice), formic acid (found in insects) and stuff like that. * Inorganic acids contain hydrogen but no carbon and are best thought of as being mineral acids. Sulfuric, phosphoric and nitric acid are the most common, taking their name from the chemicals they contain that join together with the hydrogen, which is in there as well. API 571 (Sec. 5.1.1.1) contains DMs relating to both organic and inorganic acids. Why do acids corrode metal? wwwmatthews-training.co.uk 125mi Re eee eee ere Easy. Acids are electron-grabbers. Tempt them with a loosely- held electron from a bit of metal and they will ‘accept it’, jettisoning a bit of hydrogen to make space for it. You can see this happening below. Here is a piece of zinc faced with enough hydrochloric acid (HC!) to cause it a problem. Zn +2HCI (Note how two lots of HCI are needed to make it a fair fight) Remember that the zinc may be there as a pure metal, or may be alloyed with something else (as in brass, which is a Cu/Zn mix). Now the HCl acid grabs the zinc electron, turning the pure metal into a different compound, zinc chloride (effectively, a product of corrosion), and jettisons some hydrogen, which flies off as a gas (H2). Here it is Zn +2HCl — ZnCly + Hp Now you can see the two problems. First, the corrosion compound (ZnCl), is scale or powder and so lacks any strength that the Zn metal had, so the material is weakened. The ZnCl, has also lost any other desirable proper- ties the zinc metal contributed to the original zinc alloy (e.g. brass, if that is the form it was in). * Second, the loose hydrogen that is released is free to cause all kind of problems, given its tendency to permeate where it, is not welcome, causing HIC, SSC and hydrogen blistering. (We covered these in the wet H2S DMs from API 571 (5.1.2.3).) 126 ‘www.matthews-training.co.ukSECTION Damage Mechantns Refinery ChemkcalAl/Alaline LOW (Group) mi Taken together, you can see that acid corrosion is not good news, | as far as metals are concerned. What affects the severity of acid corrosion? Fortunately, there are few surprises about the severity of acidic attack on commonly used steels in the refining industry. Fig F2 shows the situation ~ note the four main influences. ‘www.matthews-training.co.uk Wy' mh ete CAUSTIC CORROSION Description Appearance ' Mainly a boiler DM. General/ Local metal loss and grooving local corrosion under high inside boiler tubes heat transfer/evaporative conditions Inspection: Profile RTof boiler tubes. | Borescope access or tube sampling for internal visual inspection. UT thickness checking and EMAT can be unreliable under real boiler/scaling conditions. Critical factors: The most serious (grooving) damage happens | under scale deposits and on tube waterlines. Not dramatically temperature-dependent at low caustic concentrations. High-strength | solution can cause corrosion > 79°C (175°F) with corrosion rate increasing significantly > 93°C (200°) FFP/Severity: Best avoided by design, i.e. minimise scaling by providing uniform water/steam flow and | correct burner adjustment to give unform heat Il transfer flux. 128 www.matthews-training.co.ukvm Daeg i peda Caen ig nGeeeaer oe mh References: Boiler tubes can lose a lot of wall thickness and still remain within twin Code-minimum thickness. In practice, however, caustic scaling and grooving becomes increasingly localised as it progresses, resulting in tube leaks and spli These require boiler shutdown to repair/ replace. API 571 (4.3.10) See also departure from nucleate boiling (DNB), API571 (4.2.11). www.matthews-training.co.uk 129wm hata in anise I BOILER CONDENSATE/CO2 CORROSION Desci Appearance Corrosion and pitting in the Heavy pitting and localised | condensate/feed section of a corrosion/heavy pitting on pipe boiler/steam system internal surfaces Inspection: Most commonly found asa result of leaks in condensate pipes. \ UTof unreliable or thin-walled tubes with poor backwall echo from corroded internal surfaces. Feed water analysisis the best early diagnosis tool. Critical factors: Dissolved O2 isa major cause, resulting from I incorrect ‘oxygen scavenger’ chemical treatment. Normally results in pitting Dissolved CO: (absorbed into the very pure condensate at ambient temperature) causes more regular grooving corrosion. FFP/Severity: Rarely an integrity-threatening DM when in the low-pressure/temperature parts of a steam circuit. Will generally result in tube leaks and | further feed contamination. More dangerous if corrosion products contaminate the feed system de-aerator (DA) | 130 www.matthews-training.co.ukI SUCTION F: Damage Mechantsmss Refinery ChemiealAc/Alkaline LOWT (Group 5) wm oe | FIG F5 Condensate Low-Temperature Corrosion 0 + CO, etbedind ron seranvaaren — @ “TS comes oaing Baler ‘and canyover into cur es ain. Can a scale up valves sreaw ts q pe cones ir Y Ss remip corte | 05000 bac em Fe fash any : ge ‘ © erveawesacy > | pees Cea coast Feedtank Osi parlegust | www.matthews-training.co.uk BImi (Quick Guide to Damage and Corrosion Mechanisms APIS7L where they can contribute to the risk of a corrosion/cracking mechanism. References: API 571 (4.3.5). See also API 571 (4.5.2) covering corrosion fatigue. See also CO2 corrosion, API 571 (4.3.6). 132 www.matthews-training.co.ukpa Ton Saigon Ry os HAST ORT eer mK ' FLUE GAS DEWPOINT CORROSION Appearance | Sulfuric acid flue gas corrosion General wastage or pitting on boiler dewpoint temperature —_gas-side tube surfaces | (oiler back-end) | Inspection: Critical factors: FFP/Severity: | References: UT thickness of economiser and feed tube banks (may be unreliable on thin-walled, and not possible on finned tubes). Worse on high sulfur residual oil or coal fuels. Sulfuric acid (H2S0,) precipitates out of boiler flue gas below dewpoint temperature (approx. 138°C (280°F)). Corrodes LCS economiser fired tube banks. Causes ‘craze-cracking’ in 300 series SS components in the gas path (e.g. feedwater heater in HRSG type boilers) Tube leaks are a boiler efficiency/process issue rather than a major safety issue. Significant wall thinning can be accommodated in some tube banks straight sections, but the effect is worse on tube bends. API 571 (4.3.7). www.matthews-training.co.uk 133mi Quick Guide to Damage and Corrosion Mechantsns ~APLS71 | AMINE CORROSION Description Appearance Amine is used in refinery to _ General or localised corrosion remove H2S and CO2 from and LOWT process streams. LCS is corroded by CO; and H2S gases, dissolved in the amine and amine salts | Co | Inspection: VT and UT thickness measurements. i Corrosion coupons/probes. Monitoring of exchangers and filters for 1 corrosion debris. Critical factors: Most problems of amine corrosion of LCS are | caused by operating upsets or contamination. | Corrosion rates increase with temperature (approx. > 104°C (220°F)). | ‘Two-phase flow and high fluid velocities (> 6 més for lean amine) will greatly increase the speed of attack. | FFP/Severity: 300 series SS are highly resistant so do not cause FFP problems in amine service. LOWT results in leaks rather than catastrophic cracking failure. API 579 (Sec. 4.5) can be used for LOWT | assessments, once the corrosion rate has been arrested. References: API571 (5.1.1.1). | 13 ‘www.matthews-training.co.uk Icee mi | ABBREVIATIONS | The following is a list of abbreviations used in this guide and API I RP 571. ACoP Approved code of practice CSCC Carbonate alkaline stress corrosion cracking AET Acoustic emission testing Al Alut jum API American Petroleum Institute ASME American Society of Mechanical Engineers ASTM American Society for Testing of Materials AWS ‘American Welding Society | BHN Brinell hardness number (same as HB) BS British standard € Carbon Ceq Carbon equivalent CHa Methane cd Cast iron CLSCC Chloride stress corrosion cracking coz Carbon dioxide cr Chromium cs Carbon steel cu Copper ; OM Damage mechanism DNe Departure from nucleate boiling | EC Eddy current ECT Eddy current testing | EN Euronorm | ER Electrical resistance (probes) Fcc Fluid catalytic cracking www.matthews-training.co.uk 135Ki FCI Fe FFP FFS FM FMR FPS He Hs HAZ HB Hcl HE HE Hg HIC HRC HRSG HTHA, HV ID ITP KOH kPa ks Les LE MAwP MDMT MIC mm/yr Mn 136 Quick Guide to Damage and Corrosion Mechanisms—APIST1 Flake cast iron Iron Fitness for purpose (same as FFS) Fitness for service (same as FFP) Failure mode Field metallography replication Feet per second Hydrogen Hydrogen sulfide Heat affected zone Hardness (Brinell) Hydrochloric acid Hydrogen embrittlement Hydrofluoric acid Mercury Hydrogen-induced cracking Hardness Rockwell (C scale) Heat recovery steam generator High-temperature hydrogen attack Hardness (Vickers) Internal diameter Inspection and test plan Potassium hydroxide kiloPascal kilopounds per square inch Low-carbon steel Liquid metal embrittlement Maximum allowable working pressure Minimum design metal temperature Microbial-induced cracking Millimetres per year Manganese www matthews-training.co.ukAmpREMIATIONS KK | Mo | MPa MPY MT NAC NACE NaOH NB NDE NDT NHa Ni PASCC ! pce ; PD PFD pH PHSS PMI PP | PWHT RP. RT scc | seer SOHIC Molybdenum MegaPascal Mils (0.001 in) per year Magnetic testing Naphthenic acid corrosion National Association of Corrosion Engineers (USA) Sodium hydroxide National Board of Boiler and Pressure Vessel Inspec- tors (USA) Non-destructive examination Non-destructive testing Ammonia Nickel Oxygen Outer (external) diameter Polythionic acid stress corrosion cracking Post-construction code Published document Process flow diagrams Potential for hydrogen Precipitation hardenable stainless steel Positive material identification Partial pressure Penetrant testing Post-weld heat treatment Recommended practice Radiographic testing Sulfur Stress corrosion cracking Spheroidal graphite cast iron Silicon Stress oriented hydrogen-induced cracking ‘www.matthews-training.co.uk 137mi cs oaarsnayas cafe waaace-inen ss Stainless steel sscc Sulfate stress corrosion cracking TAN Total acid number Ti Titaniuum TOFD Time-of-flight diffraction uT Ultrasonic testing v Vanadium vt Visual testing WEMT Wet fluorescent magnetic testing ‘wes Weld procedure specification wt% Percentage by weight Zn Zine 138 www.matthews-training.co.uknee KK REFERENCE CODES Code/standard | Subject number! reference ‘API RP 941 Steels for high-temperature/pressure hydrogen service ‘API RP 580 Risk-based inspection (RBI) API RP 945 Avoiding environment-assisted cracking (EAC) in amine units API 660 Shell/tube heat exchangers for general refinery service NACE MR 0103 Materials resistant to sulfide stress cracking (SSC) in sour service environment NACE RP 0170 Protection of austenitic steels from polythionic SCC during shutdown ‘APIRP 579. Fitness-for-service (FFS) studies ‘APIRP939-C__| Guidance for avoiding sulfidation corrosion failures NACE SP 01472 | Preventing in-service EAC of carbon steel weldments APIRP 577 Welding inspection and metallurgy ‘WRC Bulletin 32 | Graphitisation of steels in refinery equipment NACE SP0403__| Avoiding caustic SCC in carbon steel ‘www.matthews-training,co.uk 139FIG P2 Contact us for your FREE INDUSTRY GUIDES FROM MATTHEWS ENGINEERING TRAINING We are pleased to offer these publications free of charge* to interested parties in the plant inspection and integrity industry. + Corrosion severity grades for common DMs + Pocket size A7 laminated + Summary of qualifications/certificates, in the integrity industry + Careor progression ron = + IMustrated repair procedures Pit compllant with API 810/570 Corny, $ and ASME PCC2 + Welded mechanical and composite repairs included. + Pocket size A6 laminated ‘To obtain your guides, contact us through our website ‘www.matthewstraining.co.uk “Bulk orders can be supplied for a nominal printing and shipping chargeFIG P3 MATTHEWS ENGINEERING TRAINING LTD OUR RANGE OF PUBLIC COURSES ASME PLANT INSPECTOR CERTIFICATE + ASME Plot ompector LI: 5 day residential comme * ASMP keen y + REMEPin impector12.48 ry resdeniatease — XS ME. ‘20th Pint parca acenonrmeonine NERY API CERTIFICATE PREPARATION PROGRAMME (ur API exam preparation programme has 285% pasate. APLS10 Vessc Inspection } Combined online API ‘AP1370 Pipework Inspection ‘and residential 510 ‘API 655 Storage Tank Inspection course programmes B70 + API590: Risk Based Inspection (RED Online only walning BO + API57I: Damage Mechanisms programmes 574 SPECIALIST/ADVANCED COURSES + Boller Inspection Certfeate Programme (BCIP) Sr See www.bciptraining.com / + Fimess For Service (FF): Assessment to API RP 379 days) + Non intrusive inspection (NI: DaV RP-103 (days) P INTRODUCTORY/PRACTICAL COURSES + Pressure Relief Valves (P Inspection and Maintenance (3 day workshop course) + Pressure Equlpment Repair API Codes and ASME PCC2 (3 days)FIG P4 YOUR FIRST STEP FOR IN-HOUSE COURSES MM In addition to our scheduled public courses we provide a wide variety of tailored in-house courses ‘+ More than 500 courses presented since 1999 + Course length and content to match your requirements and delegate profile ‘+ Examined or ‘appreciation’ courses available ‘As well as ASME plant inspector and API code training courses, we present individually tailored courses in: Pressure testing PSSR and PED regulations Pressure equipment code design (ASME/EN/BS) Bolting and jointing ‘New construction shop inspection Cranes and lifting equipment inspection (LOLER) + Power boiler inspection + Welding/NDT/ASME IX + PRY inspection and maintenance Contact us with your requirements for a quick response and. proposal. enquiries@matthews-training.co.ukFIG P5 Technical Publications From MATTHEWS ENGINEERING TRAININ Handbook of Mechanical Boller In Service Inspection Inspection Guide + The comprehensive guide ‘+ Inspection handbook for tothe inservice package boilers inspection of mechanical ‘Course book for Boller and pressure plant Inspector Certificate Programme (BICP) ‘+ 200 pages, AS, full colour, spiral bound APLSIO APL370 APL 653 Pressure Vessel Pipework Inspection _ Atmospheric Storage Inspection ‘Tank Inspection ‘Our popular guides have assisted delegates worldwide in passing their ‘API510/570/653 examinations, ‘These guides are priced for individual or bulk orders. Some copies are made available free of charge to our existing training customers. Contact us via our website at www.natthewstraining.co.ukey + In addition to our scheduled public courses we provide a wide variety of tailored in-house courses ‘+ More than 500 courses presented since 1999 + Course length and content to match your requirements and delegate profile + Examined or ‘appreciation’ courses available ‘As well as ASME plant inspector and API code training courses, we present individually tailored courses in: © Pressure testing ‘+ PSSR and PED regulations © Pressure equipment code design (ASME/EN/BS) * Bolting and jointing + New construction shop inspection * Power boiler inspection * Welding/NDT/ASME IX ‘+ PRV inspection and maintenance + API510/570/653 Certified Inspector courses Contact us with your requirements for a quick response and proposal, enquiries@matthewstraining.co.uk ore Re os ots pe oe